EP0729462B1 - Procede de preparation de gamma-butyrolactone - Google Patents
Procede de preparation de gamma-butyrolactone Download PDFInfo
- Publication number
- EP0729462B1 EP0729462B1 EP95900684A EP95900684A EP0729462B1 EP 0729462 B1 EP0729462 B1 EP 0729462B1 EP 95900684 A EP95900684 A EP 95900684A EP 95900684 A EP95900684 A EP 95900684A EP 0729462 B1 EP0729462 B1 EP 0729462B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dihydrofuran
- butyrolactone
- hydrogen
- catalyst
- hydrogenation catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-dihydrofuran Chemical compound C1OCC=C1 ARGCQEVBJHPOGB-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 125000004852 dihydrofuranyl group Chemical group O1C(CC=C1)* 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052702 rhenium Inorganic materials 0.000 claims description 15
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 15
- 239000012159 carrier gas Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 39
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 18
- 150000002739 metals Chemical class 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 239000012876 carrier material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- JNODDICFTDYODH-UHFFFAOYSA-N 2-hydroxytetrahydrofuran Chemical compound OC1CCCO1 JNODDICFTDYODH-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- -1 aluminum silicates Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229940116318 copper carbonate Drugs 0.000 description 2
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 150000002835 noble gases Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- VIHAEDVKXSOUAT-UHFFFAOYSA-N but-2-en-4-olide Chemical compound O=C1OCC=C1 VIHAEDVKXSOUAT-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 125000001145 hydrido group Chemical group *[H] 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to a method for manufacturing of ⁇ -butyrolactone.
- ⁇ -Butyrolactone is a chemical that is required in large quantities for example as a solvent for polyacrylonitrile, cellulose acetate, Polystyrene, shellac and resins serve and continue as Starting material for the production of economically important Products such as pyrrolidone, N-methylpyrrolidone and polyvinylpyrrolidone is used.
- the present invention was based on the object of a method to find that starting from the production of ⁇ -butyrolactone of 2,5-dihydrofuran or 2,3-dihydrofuran, to economic Way.
- a way should be found on the ⁇ -butyrolactone starting from 2,5-dihydrofuran directly, can be manufactured in a single stage.
- ⁇ -butyrolactone a method for producing ⁇ -butyrolactone was developed found, which is characterized in that one 2,5-dihydrofuran or 2,3-dihydrofuran or mixtures of the two Dihydrofurans in the gas phase in the presence of water and in Presence or absence of added hydrogen with increased Reacts temperature on a hydrogenation catalyst.
- the hydrogenation catalyst used would thus act as a dehydrogenation catalyst.
- the catalysts which can be used according to the invention are usually used in industry as hydrogenation catalysts, these catalysts are still referred to as "hydrogenation catalysts" in the context of this application, despite their dehydrating effect in the process according to the invention.
- the reaction mechanism described above is merely an attempt to explain the chemical processes taking place on the catalyst in the process according to the invention, which have not been examined in detail. This proposal for the reaction mechanism is essentially supported by the observations that both 2,5-dihydrofuran and 2,3-dihydrofuran can be used in the process according to the invention, that the process according to the invention can be carried out in the absence of added hydrogen and by the by-products found .
- 2,5-dihydrofuran or 2,3-dihydrofuran or a mixture of these compounds in the gas phase with water in a dihydrofuran / water molar ratio of generally 2: 1 to 1: 100, preferably 1: 1 to 1:50 and particularly preferably from 1: 1 to 1:10 in the presence of a hydrogenation catalyst at a Pressure of generally 0.5 to 50 bar, preferably 0.8 to 40 bar and in particular from 1 to 10 bar at a temperature of 100 to 350 ° C, preferably 130 to 330 ° C and particularly preferred from 170 to 300 ° C converted to ⁇ -butyrolactone.
- Hydrogenation catalysts can be used in the process according to the invention practically all suitable for the hydrogenation of carbonyl groups Heterogeneous catalysts are used, for example those as described in Houben-Weyl, Methods of Organic Chemistry, Volume IV, 1c, pp. 16-26, Thieme-Verlag, Stuttgart, 1980.
- the hydrogenation catalysts can in the process according to the invention in a fixed bed or mobile, e.g. in a fluidized bed, in the reactor to be ordered.
- Hydrogenation catalysts used which one or more elements of the Groups Ib, VIb, VIIb and VIIIb of the Periodic Table of the Elements contain. These catalysts can continue to promote their catalytic activity and selectivity or several elements from groups Ia, IIa, IIIa, IVa and Va of the Periodic Table of the Elements.
- Preferred Catalysts are especially those that are catalytically active Components e.g. Copper, chrome, rhenium, cobalt, nickel, Rhodium, ruthenium, iridium, palladium, iron or platinum or Mixtures of several of these elements and, if appropriate, as further, influencing their catalytic activity and selectivity Components e.g. Contain indium, tin or antimony.
- Hydrogenation catalysts are preferred in the process according to the invention used that contain rhenium and / or copper.
- Heterogeneous catalysts can be used in the process according to the invention both so-called precipitation catalysts and conventional ones Supported catalysts are used, which by applying the catalytically active component produced on a support material have been.
- the precipitation catalysts can be prepared by their catalytically active components from their salt solutions, in particular from the solutions of their nitrates and / or acetates by adding solutions of alkali metal and / or alkaline earth metal hydroxide and / or carbonate solutions, e.g.
- Precipitates hydroxides, oxide hydrates, basic salts or carbonates then the resulting precipitate dries and then by calcination at generally 300 to 700 ° C, in particular 400 to 600 ° C in the corresponding oxides, mixed oxides and / or mixed valence Converts oxides, which by treatment with gases containing hydrogen or hydrogen in the Rule 50 to 700 ° C, especially at 100 to 400 ° C to the concerned Metals and / or oxidic compounds with a low oxidation state reduced and in their actual, catalytically active Form to be transferred.
- gases containing hydrogen or hydrogen in the Rule 50 to 700 ° C, especially at 100 to 400 ° C to the concerned Metals and / or oxidic compounds with a low oxidation state reduced and in their actual, catalytically active Form to be transferred.
- gases containing hydrogen or hydrogen in the Rule 50 to 700 ° C, especially at 100 to 400 ° C to the concerned Metals and / or oxidic compounds with a low oxidation state reduced and in
- Precipitation catalysts which contain a support material can Precipitation of the catalytically active components in the presence of the relevant one Carrier material take place.
- the catalytically active components can be advantageous but also simultaneously with the Carrier material can be precipitated from the relevant salt solutions.
- Suitable carrier materials are e.g. the oxides of aluminum, of titanium, zinc oxide, zirconium dioxide, silicon dioxide, clays, e.g. Montmorrillonite, silicates, such as magnesium or aluminum silicates or zeolites such as ZSM-5 or ZSM-10 zeolites. It can mixtures of such carrier materials can also be used.
- the dried precipitate from the precipitation before calcination with molding aids such as graphite, talc or stearin, and / or with pore formers such as cellulose, methyl cellulose, Starch, wax, paraffin and / or a polyalkylene glycol, added and to shaped catalyst bodies such as tablets, spheres, Rings or strands are pressed or extruded.
- molding aids such as graphite, talc or stearin, and / or with pore formers such as cellulose, methyl cellulose, Starch, wax, paraffin and / or a polyalkylene glycol
- Hydrogenation catalysts are preferred in the process according to the invention used which the metals catalyzing the hydrogenation or metal compounds deposited on a carrier material contain.
- the metals catalyzing the hydrogenation or metal compounds deposited on a carrier material contain.
- the catalysts mentioned above which in addition to the catalytically active components contain a carrier material are suitable for the invention Processes generally support such catalysts well, where the catalytically active components e.g. applied to a carrier material by impregnation are.
- the way in which the catalytically active metals are applied to the Carrier is usually not critical and can be in a variety of ways Way to be accomplished.
- the catalytically active Metals can be e.g. by impregnation with solutions or suspensions of the salts or oxides of the concerned Elements, drying and subsequent reduction of the Metal compounds to the metals or compounds concerned lower oxidation level by means of a reducing agent, for example with hydrogen, gases containing hydrogen or Hydrazine, preferably with gases containing hydrogen, applied become.
- a reducing agent for example with hydrogen, gases containing hydrogen or Hydrazine, preferably with gases containing hydrogen, applied become.
- the reduction of those deposited on the carrier material Metal compounds can be made under the same conditions take place as described above for the precipitation catalysts were.
- the content of the supported catalysts in the catalytically active metals is in principle for the success of the invention Procedure not critical. It is understood by the expert of even that higher levels of these supported catalysts are catalytic active metals lead to higher space-time conversions can as lower levels.
- supported catalysts used the content of catalytically active metals 0.1 to 90% by weight, preferably 0.5 to 40% by weight on the entire catalyst. Because this salary refer to the entire catalyst including the support material, the different carrier materials, however, are very different specific weights and specific surfaces this information can also be exceeded or fallen short of, without this adversely affecting the result of the method according to the invention affects. Of course you can also several of the catalytically active metals on the respective Carrier material can be applied.
- the catalytic active metals for example according to the method of DE-A 25 19 817, EP-A 147 219 and EP-A 285 420 applied to the carrier become.
- the catalytically active metals as alloys which can be achieved by thermal treatment and / or reduction of e.g. salts or complexes deposited on a support by impregnation of the aforementioned metals.
- the oxides of aluminum, of titanium, zinc oxide, zirconium dioxide, silicon dioxide, Clays, e.g. Montmorillonite, silicates, such as magnesium or Aluminum silicates, zeolites such as ZSM-5 or ZSM-10 zeolites, and Activated carbon can be used.
- Preferred carrier materials are aluminum oxides, titanium dioxide, silicon dioxide, zirconium dioxide or activated carbon. Mixtures can of course also be used various carrier materials as carriers for the in the invention Process hydrogenation catalysts used.
- hydrogenation catalysts which can be used in the process according to the invention: Platinum on activated carbon, palladium on activated carbon, palladium on aluminum oxide, cobalt on activated carbon, cobalt on silicon dioxide, cobalt on aluminum oxide, iron on activated carbon, manganese on activated carbon, rhenium on activated carbon, rhenium on silicon dioxide, rhenium / tin on activated carbon, rhenium / palladium on Activated carbon, copper on activated carbon, copper on silicon dioxide, copper on aluminum oxide, copper chromite and the catalysts according to DE-A 392 332, US-A 3 449 445, EP-A 44 444, EP-A 147 219, DE-A 39 04 083 , DE-A 23 21 101, EP-A 415 202, DE-A 23 66 264 and EP-A 100 406.
- Particularly preferred catalysts contain at least one of the Metals copper or rhenium.
- Precipitation catalysts containing copper can generally 0.1 to 90 wt .-%, preferably 1 to 80 wt .-% and particularly preferably 5 to 50 wt .-% copper, calculated as CuO and based on the total weight of the catalyst, contain.
- Copper-containing, through impregnation or coating a supported material can be produced in the generally 0.1 to 30% by weight, preferably 1 to 30% by weight and particularly preferably 3 to 25% by weight of copper, calculated as CuO and based on the total weight of the catalyst.
- Containing rhenium Catalysts are used in the process according to the invention preferably used in the form of supported catalysts, the rhenium, calculated as Re and based on the total weight of the catalyst, in amounts of 0.1 to 25% by weight, preferably of 1 Contain up to 20 wt .-% and particularly preferably from 2 to 10 wt .-%.
- the process according to the invention is advantageously continuous exercised.
- tubular reactors in which the Catalyst is advantageously arranged in the form of a fixed bed, or fluidized bed reactors in which the catalyst passes through the Gas flow is moved to be used.
- the starting materials 2,5-dihydrofuran and / or 2,3-dihydrofuran and water can, for example, be converted into the gas phase in an evaporator before they are passed over the catalyst.
- the starting materials are advantageously evaporated in a carrier gas stream, it being possible, for example, to use noble gases, nitrogen, C 1 -C 4 -hydrocarbons, preferably methane and preferably hydrogen, as carrier gases.
- the carrier gas stream is metered in such a way that the starting materials, products and any by-products formed, for example 1,4-butanediol, tetrahydrofuran and butanol, remain gaseous in the reactor.
- the carrier gas stream used to evaporate the starting materials can be advantageous also be guided in a circle, i.e. after deposition of the products contained in it after leaving the catalyst bed, for example in a gas-liquid separator or Cooler, reused for evaporation of the starting materials as a carrier gas stream become. If no gas cycle mode is used or If a carrier gas other than hydrogen is used, then that is sufficient released in the reaction according to equation (3) on the catalyst Hydrogen to keep the hydrogenation catalyst active.
- the catalysts in the process according to the invention are charged with 0.05 to 5 kg of dihydrofuran / 1 catalyst ⁇ h -1 , preferably with 0.1 to 3 kg of dihydrofuran / 1 catalyst ⁇ h -1 .
- the gaseous reactor discharge can after cooling and condensation of the products by conventional distillation be worked up, for example by fractional distillation. It is also possible to discharge the gaseous reaction direct to a distillation column.
- by-products contained in the reactor discharge such as 1,4-butanediol, tetrahydrofuran and / or n-butanol, as valuable products be won.
- Any contained in the reactor discharge 2,5- and / or 2,3-dihydrofuran and / or water can be used in the Distillation separated from the product and again, after evaporation, be returned to the reactor.
- the method according to the invention thus enables starting from 2,5-dihydrofuran and / or 2,3-dihydrofuran the economic Production of ⁇ -butyrolactone. It is particularly advantageous that ⁇ -butyrolactone generated in one step from 2,5-dihydrofuran can be.
- the starting material 2,5-dihydrofuran used according to the invention can by isomerization of vinyloxirane, for example after the processes according to US-A 5,034,545 and US-A 5,082,956 become.
- 2,3-dihydrofuran can be made from 2,5-dihydrofuran its base-catalyzed or photochemically catalyzed isomerization, for example according to the methods of Paul et al. (Bull. Soc. Chim. France 668 (1950)) or Hubert et al. (J. Chem. Soc. Perkin II 366 (1972)).
- 102 g were placed in a 160 ml gas phase reactor with external heating a supported copper-on-silica catalyst (copper content: 22% by weight, calculated as CuO and based on the total weight the catalyst; made by impregnating the wearer with an ammoniacal copper carbonate solution, drying the impregnated Carrier at 120 ° C and calcination at 500 ° C) in the form filled with grit and in a stream of hydrogen at one temperature from an initial 150 ° C and a final temperature of 250 ° C.
- a supported copper-on-silica catalyst copper content: 22% by weight, calculated as CuO and based on the total weight the catalyst; made by impregnating the wearer with an ammoniacal copper carbonate solution, drying the impregnated Carrier at 120 ° C and calcination at 500 ° C
- Example 2 Analogously to Example 1, 15 ml / h of 2,5-dihydrofuran and 32 ml / h of water at 220 ° C. over 149 g of a catalyst containing copper and magnesium on silicon dioxide (composition: copper, calculated as CuO: 43.0% by weight ; Magnesium, calculated as MgO: 18.0% by weight; Silicate, calculated as SiO 2 : 35.0% by weight; Barium, calculated as BaO: 1% by weight; Chromium, calculated as Cr 2 O 3 : 0.6% by weight; zinc, calculated as ZnO: 0.4% by weight; sodium, calculated as Na 2 O: 0.2% by weight; the rest is predominantly carbonate; all data based on the Total weight of the catalyst; produced by a common precipitation from a solution of the metal salts and sodium silicate (water glass) with sodium carbonate, drying of the precipitate obtained, extrusion to strands with talc as a shaping aid and calcination at 500 ° C, reduction analogous to Example
- Example 2 Analogously to Example 1, 19 ml / h of 2,5-dihydrofuran and 11 ml / h Water passed over 142 g of the catalyst from Example 2. At a conversion of 99.7% was ⁇ -butyrolactone with a Selectivity of 89% obtained (2,3-dihydrofuran: 0.13%; furan: 3.9%; Tetrahydrofuran: 5%; n-butanol: 1.7%; Rest: small amounts different, not balanced low boilers).
- Example 2 Analogously to Example 1, 8 ml / h of 2,5-dihydrofuran and 15 ml / h of water at 210 ° C over 85 g of a copper on activated carbon catalyst (Copper content: 10% by weight, calculated as CuO and based on the Total weight of the catalyst; made by impregnation of 4 mm activated carbon strands with ammoniacal copper carbonate solution; Drying at 120 ° C and reduction analogously to Example 1) passed.
- a copper on activated carbon catalyst Copper content: 10% by weight, calculated as CuO and based on the Total weight of the catalyst; made by impregnation of 4 mm activated carbon strands with ammoniacal copper carbonate solution; Drying at 120 ° C and reduction analogously to Example 1.
- Example 2 Analogously to Example 1, 10 ml / h of 2,5-dihydrofuran and 9 ml / h of water were added over 73 g of a rhenium on activated carbon catalyst (rhenium content: 6% by weight, calculated as Re; produced by impregnating 4 mm activated carbon strands with an aqueous dirhenium heptoxide (Re 2 O 7 ) solution; drying at 120 ° C; reduction analogous to Example 1).
- rhenium content 6% by weight, calculated as Re
- Re 2 O 7 aqueous dirhenium heptoxide
- ⁇ -butyrolactone was formed with a selectivity of 91% (2,3-dihydrofuran: 0.5%; furan: 1%; tetrahydrofuran: 5%; n-butanol: 1%; rest: small amounts various, not balanced low boilers).
- activated carbon catalyst was used over the rhenium 14 ml / h of 2,5-dihydrofuran and 24 ml / h of water passed at 220 ° C.
- ⁇ -butyrolactone was added with a Selectivity of 87% formed (furan: 2.5%; tetrahydrofuran: 9%; n-butanol: 1%; Rest: various, not accounted for Low boilers).
- Example 5 Analogously to Example 1, 10 ml / h of 2,3-dihydrofuran and 8 ml / h of water at 220 ° C in a carrier gas stream of 13 l / h of hydrogen 47 g of the rhenium on activated carbon catalyst passed according to Example 5 (Reactor volume: 100 ml). With sales of 99.5% ⁇ -butyrolactone was formed with a selectivity of 98% (Tetrahydrofuran: 0.3%; 4-hydroxybutyraldehyde: 0.5%; rest: low Quantities of different, off-balance low boilers).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Furan Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Polyesters Or Polycarbonates (AREA)
Claims (10)
- Procédé de préparation de γ-butyrolactone, caractérisé en ce que l'on fait réagir à hautes températures sur un catalyseur d'hydrogénation, du 2,5-dihydrofurane ou du 2,3-dihydrofurane ou des mélanges de ces deux dihydrofuranes, en phase gazeuse en présence d'eau et en présence ou en l'absence d'hydrogène ajouté.
- Procédé selon la revendication 1, caractérisé en ce que l'on mène la réaction en présence d'hydrogène ajouté.
- Procédé selon les revendications 1 ou 2, caractérisé en ce que l'on mène la réaction en présence d'hydrogène ajouté et où l'hydrogène sert de gaz porteur.
- Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'on mène la réaction à une température de 100-350°C et sous une pression de 0,5-50 bar.
- Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que l'on utilise un catalyseur d'hydrogénation contenant au moins un élément choisi dans les groupes Ib, VIb, VIIb et/ou VIII de la classification périodique des éléments.
- Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'on utilise un catalyseur d'hydrogénation contenant, en plus d'au moins un élément choisi dans les groupes Ib, VIb, VIIb et/ou VIII de la classification périodique des éléments, au moins un autre élément choisi dans les groupes IIb, Ia, IIa, IIIa, Va et/ou VIa de la classification périodique des éléments.
- Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'on utilise un catalyseur d'hydrogénation contenant du rhénium.
- Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'on utilise un catalyseur d'hydrogénation contenant du cuivre.
- Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que l'on utilise un catalyseur supporté en tant que catalyseur d'hydrogénation.
- Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que l'on réduit le catalyseur d'hydrogénation avant le début de la réaction, à l'aide d'hydrogène ou de gaz contenant de l'hydrogène.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4339269 | 1993-11-18 | ||
DE4339269A DE4339269A1 (de) | 1993-11-18 | 1993-11-18 | Verfahren zur Herstellung von gamma-Butyrolacton |
PCT/EP1994/003683 WO1995014010A1 (fr) | 1993-11-18 | 1994-11-09 | PROCEDE DE PREPARATION DE η-BUTYROLACTONE |
Publications (2)
Publication Number | Publication Date |
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EP0729462A1 EP0729462A1 (fr) | 1996-09-04 |
EP0729462B1 true EP0729462B1 (fr) | 1999-02-24 |
Family
ID=6502819
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Application Number | Title | Priority Date | Filing Date |
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EP95900684A Expired - Lifetime EP0729462B1 (fr) | 1993-11-18 | 1994-11-09 | Procede de preparation de gamma-butyrolactone |
Country Status (14)
Country | Link |
---|---|
US (1) | US5646307A (fr) |
EP (1) | EP0729462B1 (fr) |
JP (1) | JP3411285B2 (fr) |
KR (1) | KR100326495B1 (fr) |
CN (1) | CN1058493C (fr) |
AT (1) | ATE176908T1 (fr) |
AU (1) | AU8141294A (fr) |
CA (1) | CA2176587C (fr) |
DE (2) | DE4339269A1 (fr) |
ES (1) | ES2128030T3 (fr) |
FI (1) | FI962046A (fr) |
RU (1) | RU2138491C1 (fr) |
TW (1) | TW360649B (fr) |
WO (1) | WO1995014010A1 (fr) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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DE19636066A1 (de) * | 1996-09-05 | 1998-03-12 | Basf Ag | Verfahren zur Dehydrierung von 1,4-Butandiol zu gamma-Butyrolacton |
JP4483156B2 (ja) * | 2002-03-28 | 2010-06-16 | 三菱化学株式会社 | ガンマブチロラクトンの精製方法 |
KR101103512B1 (ko) * | 2009-11-25 | 2012-01-09 | 에스케이종합화학 주식회사 | 1,4-부탄디올로부터 n-메틸 피롤리돈의 제조방법 |
CN103204835B (zh) * | 2012-01-13 | 2015-07-29 | 中国石油化工股份有限公司 | 一种丁内酯的制备方法 |
CN103288786B (zh) * | 2012-02-29 | 2015-03-18 | 中国石油化工股份有限公司 | 一种四氢呋喃氧化的方法 |
RU2537349C2 (ru) * | 2013-03-29 | 2015-01-10 | Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук | Способ получения 3-алкилдигидрофуран-2(3н)-онов |
JPWO2021045153A1 (fr) * | 2019-09-06 | 2021-03-11 | ||
CN115779957B (zh) * | 2022-12-10 | 2024-03-19 | 南通格瑞凯泰工程技术有限公司 | 1,4-丁二醇低压脱氢制γ-丁内酯用催化剂及其应用 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CA1139785A (fr) * | 1979-09-04 | 1983-01-18 | Johannes A.M. Van Broekhoven | Hydrolyse d'allylether et cetones ainsi preparees |
RO91930B1 (ro) * | 1985-03-14 | 1987-07-01 | Institutul De Cercetari Chimice | Procedeu pentru prepararea y-butirolactonei |
DE3926147A1 (de) * | 1989-08-08 | 1991-02-14 | Basf Ag | Verfahren zur herstellung von 2,5-dihydrofuranen |
US5082956A (en) * | 1990-03-08 | 1992-01-21 | Eastman Kodak Company | Isomerization of epoxyalkenes to 2,5-dihydrofurans |
-
1993
- 1993-11-18 DE DE4339269A patent/DE4339269A1/de not_active Withdrawn
-
1994
- 1994-11-09 US US08/640,879 patent/US5646307A/en not_active Expired - Lifetime
- 1994-11-09 JP JP51419695A patent/JP3411285B2/ja not_active Expired - Fee Related
- 1994-11-09 KR KR1019960702559A patent/KR100326495B1/ko not_active IP Right Cessation
- 1994-11-09 WO PCT/EP1994/003683 patent/WO1995014010A1/fr active IP Right Grant
- 1994-11-09 AU AU81412/94A patent/AU8141294A/en not_active Abandoned
- 1994-11-09 CA CA002176587A patent/CA2176587C/fr not_active Expired - Fee Related
- 1994-11-09 ES ES95900684T patent/ES2128030T3/es not_active Expired - Lifetime
- 1994-11-09 AT AT95900684T patent/ATE176908T1/de not_active IP Right Cessation
- 1994-11-09 EP EP95900684A patent/EP0729462B1/fr not_active Expired - Lifetime
- 1994-11-09 DE DE59407851T patent/DE59407851D1/de not_active Expired - Lifetime
- 1994-11-09 CN CN94194193A patent/CN1058493C/zh not_active Expired - Fee Related
- 1994-11-22 TW TW083110857A patent/TW360649B/zh not_active IP Right Cessation
-
1996
- 1996-05-14 FI FI962046A patent/FI962046A/fi not_active IP Right Cessation
- 1996-06-17 RU RU96113048A patent/RU2138491C1/ru not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
RU2138491C1 (ru) | 1999-09-27 |
KR960705801A (ko) | 1996-11-08 |
KR100326495B1 (ko) | 2002-11-27 |
CN1058493C (zh) | 2000-11-15 |
DE4339269A1 (de) | 1995-05-24 |
JPH09505067A (ja) | 1997-05-20 |
FI962046A0 (fi) | 1996-05-14 |
JP3411285B2 (ja) | 2003-05-26 |
EP0729462A1 (fr) | 1996-09-04 |
WO1995014010A1 (fr) | 1995-05-26 |
ES2128030T3 (es) | 1999-05-01 |
AU8141294A (en) | 1995-06-06 |
TW360649B (en) | 1999-06-11 |
US5646307A (en) | 1997-07-08 |
ATE176908T1 (de) | 1999-03-15 |
FI962046A (fi) | 1996-05-14 |
DE59407851D1 (de) | 1999-04-01 |
CN1135213A (zh) | 1996-11-06 |
CA2176587C (fr) | 2004-05-25 |
CA2176587A1 (fr) | 1995-05-26 |
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